Journal of Physical Chemistry A, Vol.102, No.35, 6973-6980, 1998
A theoretical and experimental study of the CN+NO association reaction
A pulsed-laser photolysis/laser-induced fluorescence technique is employed in the determination of the pressure and temperature dependence of the reaction of CN with NO in the range from 207 to 740 K and for Ar bath gas pressures ranging from 30 to 900 Torr. A variational RRKM model coupled with a one-dimensional master equation treatment provides a reasonably satisfactory description of the available kinetic data for both the association and dissociation processes. The association kinetic data is best fit by a collisional energy transfer parameter, [Delta E](down), for the simple exponential down model, which gradually increases from -35 cm(-1) at 100 K to -500 cm(-1) at 740 K. The expression 3.4 x 10(-10) exp(120/T) cm(3) s(-1) reproduces the present theoretical estimates for the high-pressure rate constant in the range from 207 to 740 K.
Keywords:THERMAL UNIMOLECULAR REACTIONS;FLEXIBLE TRANSITION-STATES;COLLISION RATE CONSTANTS;FALL-OFF RANGE;GAUSSIAN-2 THEORY;REACTION COORDINATE;NCNO;NO;DISTRIBUTIONS;ENERGIES